WO2004033697A2 - Method of removing entrained sulfuric acid from alkylate - Google Patents
Method of removing entrained sulfuric acid from alkylate Download PDFInfo
- Publication number
- WO2004033697A2 WO2004033697A2 PCT/US2003/029193 US0329193W WO2004033697A2 WO 2004033697 A2 WO2004033697 A2 WO 2004033697A2 US 0329193 W US0329193 W US 0329193W WO 2004033697 A2 WO2004033697 A2 WO 2004033697A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alkylation
- process according
- column
- sulfuric acid
- effluent
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/56—Addition to acyclic hydrocarbons
- C07C2/58—Catalytic processes
- C07C2/62—Catalytic processes with acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/20—Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
- C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-
- C07C2527/054—Sulfuric acid or other acids with the formula H2Sn03n+1
Definitions
- the present invention relates to the treatment of alkylate product from a process wherein normal olefins are reacted with isoalkanes in the presence of sulfuric acid to produce alkylate product. More particularly the invention relates to a process wherein the effluent from the alkylation reactor is passed through a deentrainment device to remove sulfuric acid by coalescence and subsequently treated to remove sulfonates and sulfonic esters.
- Alkylation is the reaction of a paraffin, usually isoparaffins, with an olefin in the presence of a strong acid which produces paraffins, e.g., of higher octane number than the starting materials and which boil in range of gasolines.
- a strong acid which produces paraffins, e.g., of higher octane number than the starting materials and which boil in range of gasolines.
- the reaction is generally the reaction of a C 2 to C 5 olefin with isobutane.
- hydrofluoric or sulfuric acid catalysts are most widely used under low temperature conditions. Low temperature or cold acid processes are favored because side reactions are minimized. In the traditional process the reaction is carried out in a reactor where the hydrocarbon reactants are dispersed into a continuous acid phase.
- U.S. Patent Nos. 5,420,093 and 5,444,175 sought to combine the particulate contact material and the catalyst by impregnating a mineral or organic support particulate with sulfuric acid.
- Various static systems have been proposed for contacting liquid/liquid reactants, for example U.S. Patent No. 3,496,996; 3,839,487; 2,091 ,917; and 2,472,578.
- the most widely used method of mixing catalyst and reactants is the use of various arrangements of blades, paddles, impellers and the like that vigorously agitate and blend the components together, for example, see U.S. Pat. Nos. 3,759,318; 4,075,258 and 5,785,933.
- the invention comprises removing the sulfuric acid from the alkylate by mechanical means instead of water wash or caustic treatment product prior to separating the unreacted isobutane in a deisobutanizer (DIB) column, preferably to produce alkylate having a water content of less than 100 ppm.
- the preferred mechanical means comprises a vessel containing a coalescer material upon which the sulfuric acid impinges. The sulfuric acid, being much heavier than the hydrocarbon, falls out and may be removed by gravity.
- the alkylate product is then treated in a debutanizer (DB) column to simultaneously separate the normal butane from the product and remove sulfur contaminants such as sulfonates or sulfonic esters which are by-products from the alkylation.
- DB debutanizer
- the lower end, or stripping section, of the debutanizer (DB) is packed with a hydrodesulfurization catalystwhich hydrogenates the sulfur compounds to hydrogen sulfide which can be removed with the butane overheads.
- hydrodesulfurization catalyst is placed in the stripping section of the deisobutanizer (DIB) column and the trace hydrogen sulfide is simply recycled back to the alkylation reactor which is capable of handling this corrosive material.
- DIB deisobutanizer
- the effluent from the mechanical separation is fed to a standard down flowfixed bed reactor containing a hydrodesulfurization catalyst and the hydrogen sulfide produced is removed in the overheads from the deisobutanizer (DIB) column and recycled to the alkylation reactor.
- DIB deisobutanizer
- hydrodesulfurization catalyst may be replaced with a decomposition type catalyst, such as palladium, to decompose the sulfonates and sulfonic esters to their constituent components.
- a decomposition type catalyst such as palladium
- FIG. 1 is a simplified flow diagram in schematic form of one embodiment of the invention.
- FIG.2 is a simplified flow diagram in schematic form of a second embodiment of the invention.
- FIG. 3 is a simplified flow diagram in schematic form of a third embodiment of the invention.
- the alkylate product to be treated may come from any cold acid alkylation process which uses sulfuric acid as the catalyst.
- the fluid system comprises a liquid and is maintained at about its boiling point in the reaction zone.
- the alkylate from the alkylation process contains some sulfuric acid as well as sulfonates and sulfonic esters which must be removed.
- FIG. 1 a simplified flow diagram of one embodiment is shown.
- the alkylate is taken from alkylation reactor 10 via flow line 101 and fed to deentrainment vessel 20.
- Deentrainment vessel 20 contains a coalescer material upon which the sulfuric acid droplets impinge and fall out.
- the sulfuric acid and hydrocarbons in the alkylate product are practically insoluble in one another.
- the sulfuric acid droplets are collected and recycled to the alkylation reactor 10 via flow line 104.
- the coalescer comprises a conventional liquid-liquid coalescer of a type which is operative for coalescing vaporized liquids. These are commonly known as “mist eliminators" or
- a suitable coalescer comprises a mesh such as a co-knit wire and fiberglass mesh.
- a mesh such as a co-knit wire and fiberglass mesh.
- a 90 needle tubular co-knit mesh of wire and fiberglass such as manufactured by Amistco Separation Products, Inc of Alvin, Texas or ACS Industries LLC of Houston, Texas, can be effectively utilized, however, it will be understood that various other materials such as co-knit wire and teflon (Dupont TM), steel wool, polypropylene, PVDF, polyester or various other co-knit materials can also be effectively utilized in the apparatus.
- Various wire screen type packings may be employed where the screens are woven rather than knitted.
- Other acceptable coalescers include perforated sheets and expanded metals, open flow cross channel structures which are co-woven with fiberglass or other materials, such as polymers.
- the liquid hydrocarbon material from the deentrainment vessel is passed to a deisobutanizer (DIB) column 30 via flow line 102 having distillation structure 32 where the isobutane is removed as overheads via flow line 104 and recycled to the alkylation reactor.
- the alkylate and normal butane are removed from the deisobutanizer (DIB) column 30 as bottoms via flow line 105 and fed to a debutanizer (DB) column 40 containing a bed 44 of hydrodesulfurization catalyst in the stripping section and standard distillation structure 42 in the remainder of the column. Hydrogen is fed via flow line 108.
- the sulfonates and sulfonic esters are converted to hydrogen sulfide by the catalyst which is removed in the overheads via flow line 106 along with the normal butane plus trace amounts of H 2 S or in the embodiment wherein the catalyst bed 44 contains a decomposition catalyst trace amounts of SO 2 and SO 3 .
- the alkylate product is removed as bottoms via flow line 107.
- Catalysts which are useful for the hydrodesulfurization reaction include Group VIII metals such as cobalt, nickel, palladium, alone or in combination with other metals such as molybdenum or tungsten on a suitable support which may be alumina, silica-alumina, titania-zirconia or the like. Normally the metals are provided as the oxides of the metals supported on extrudates or spheres and as such are not generally useful as distillation structures.
- the catalysts may additionally contain components from Group V and VIB metals of the Periodic Table or mixtures thereof.
- the use of the distillation system reduces the deactivation and provides for longer runs than the fixed bed hydrogenation units of the prior art.
- the Group VIII metal provides increased overall average activity.
- Catalysts containing a Group VIB metal such as molybdenum and a Group VIII such as cobalt or nickel are preferred.
- Catalysts suitable for the hydrodesulfurization reaction include cobalt-molybdenum, nickel-molybdenum and nickel-tungsten.
- the metals are generally present as oxides supported on a neutral base such as alumina, silica-alumina or the like. The metals are reduced to the sulfide either in use or prior to use by exposure to sulfur compound containing streams.
- the catalyst typically is in the form of extrudates having a diameter of 1/8, 1/16 or 1/32 inches and an L/D of 1.5 to 10.
- the catalyst also may be in the form of spheres having the same diameters. In their regular form they form too compact a mass and are preferably prepared in the form of a catalytic distillation structure.
- the catalytic distillation structure must be able to function as catalyst and as mass transfer medium.
- FIG. 2 A second embodiment is shown in FIG. 2 wherein the hydrodesulfurization catalyst is placed in a bed 34 within the deisobutanizer (DIB). Hydrogen is fed to the deisobutanizer (DIB) via flow line 108.
- DIB deisobutanizer
- the hydrogen sulfide is taken in the overheads via flow line 104 along with the isobutane which is recycled to the alkylation reactor 20. Excess hydrogen and trace impurities are removed via flow line 109 or in the embodiment wherein the catalyst bed 34 contains a decomposition catalyst, trace amounts of SO 2 and SO 3 .
- the metallurgy of the alkylation reactor is capable of handling the corrosive hydrogen sulfide.
- nC 4 is shown being removed in a separate tower, it may alternatively be removed as a sidedraw in the DIB tower 30 either above or below the catalyst bed 34.
- N-C 4 is removed in the overheads via flow line 106 along with the normal butane plus trace amounts of H 2 S
- the alkylate product is removed as bottoms via flow line 107.
- FIG. 3 A third embodiment is shown in FIG. 3 wherein the hydrodesulfurization catalyst is placed in a bed 52 contained within standard downflow trickle bed reactor 50 immediately following the deentrainment vessel preceding the DIB column. Hydrogen is fed to this reactor via flow line 108. The effluent from the reactor 50 is fed to the DIB column via flow line 110. Again the remainder of the reference numerals are identical to those in FIG.'s 1 and 2. The trace amounts of hydrogen sulfide are removed in the overheads from the deisobutanizer (DIB) 30 via flow line 104 along with the isobutane, both being recycled to the alkylation reactor 10.
- DIB deisobutanizer
- the hydrodesulfurization catalyst may be replaced with a decomposition catalyst such as palladium, which reduces the sulfonates and sulfonic esters to their constituent elements.
- a decomposition catalyst such as palladium, which reduces the sulfonates and sulfonic esters to their constituent elements.
- the sulfur compounds instead of trace H 2 S the sulfur compounds are SO 2 and SO 3 .
- the use of the deentrainment vessel with the coalescing material effectively removes the sulfuric acid and removes the necessity of either water wash or caustic treatment of the product from the alkylation reactor.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002501305A CA2501305A1 (en) | 2002-10-11 | 2003-09-17 | Method of removing entrained sulfuric acid from alkylate |
JP2004543308A JP2006502282A (en) | 2002-10-11 | 2003-09-17 | Method for removing entrained sulfuric acid from alkylate |
EP03749730A EP1558549A2 (en) | 2002-10-11 | 2003-09-17 | Method of removing entrained sulfuric acid from alkylate background of the invention |
AU2003267259A AU2003267259A1 (en) | 2002-10-11 | 2003-09-17 | Method of removing entrained sulfuric acid from alkylate background of the invention |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/269,261 | 2002-10-11 | ||
US10/269,261 US6852902B2 (en) | 2002-03-15 | 2002-10-11 | Method of removing entrained sulfuric acid from alkylate |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2004033697A2 true WO2004033697A2 (en) | 2004-04-22 |
WO2004033697A3 WO2004033697A3 (en) | 2005-02-24 |
Family
ID=32092422
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2003/029193 WO2004033697A2 (en) | 2002-10-11 | 2003-09-17 | Method of removing entrained sulfuric acid from alkylate |
Country Status (9)
Country | Link |
---|---|
US (3) | US6852902B2 (en) |
EP (1) | EP1558549A2 (en) |
JP (1) | JP2006502282A (en) |
KR (1) | KR20050055755A (en) |
CN (1) | CN100488922C (en) |
AU (1) | AU2003267259A1 (en) |
CA (1) | CA2501305A1 (en) |
WO (1) | WO2004033697A2 (en) |
ZA (1) | ZA200501976B (en) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6852902B2 (en) * | 2002-03-15 | 2005-02-08 | Catalytic Distillation Technologies | Method of removing entrained sulfuric acid from alkylate |
US7119244B2 (en) * | 2005-01-13 | 2006-10-10 | Catalytic Distillation Technologies | Method of removing organic sulfur compounds from alkylate |
US8246921B2 (en) * | 2008-09-24 | 2012-08-21 | Uop Llc | Alkylation unit |
DE102009004655B4 (en) | 2009-01-15 | 2013-02-14 | Oxea Gmbh | Process for the preparation of aldehydes |
US9567533B2 (en) * | 2011-02-02 | 2017-02-14 | Basf Se | Process for separation of water from pyrolysis gasoline |
US9458068B2 (en) | 2012-12-10 | 2016-10-04 | Uop Llc | Process and vessel for removing one or more sulfur compounds |
US9233319B2 (en) | 2012-12-10 | 2016-01-12 | Uop Llc | Apparatus and process for contacting liquids |
US8813976B2 (en) | 2012-12-10 | 2014-08-26 | Uop Llc | Process and apparatus for extracting |
US9457294B2 (en) | 2012-12-10 | 2016-10-04 | Uop Llc | Apparatus and process for contacting and separating liquids |
CN103952178B (en) * | 2014-05-13 | 2016-01-06 | 山东金诚重油化工技术研究院 | A kind of method shortening sulfuric acid alkylation unit on-stream time |
CN105670686B (en) * | 2016-03-04 | 2017-09-12 | 华东理工大学 | The method and apparatus of alkylated reaction effluent pickling |
CN108328696A (en) * | 2017-01-20 | 2018-07-27 | 宝山钢铁股份有限公司 | A kind of preparation method of the compound coalescence material of modified Teflon for metallurgical emulsifying liquid waste water de-oiling |
CN109266377B (en) * | 2018-11-28 | 2021-08-10 | 华东理工大学 | Method and device for self-heating flash evaporation of sulfuric acid alkylation reaction product |
WO2021095329A1 (en) * | 2019-11-13 | 2021-05-20 | 株式会社トクヤマ | Hydrogen chloride dehydration method |
CN112920844B (en) * | 2021-01-20 | 2022-01-07 | 华东理工大学 | Device and method for improving quality of alkylated oil product |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3013093A (en) * | 1957-03-20 | 1961-12-12 | Kellogg M W Co | Alkylation process |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2091917A (en) | 1933-09-06 | 1937-08-31 | Pennsylvania Petroleum Res Cor | Apparatus for treating mineral oils |
US2472578A (en) | 1946-03-21 | 1949-06-07 | Atlantic Refining Co | Method of contacting fluids |
US2762853A (en) * | 1954-06-08 | 1956-09-11 | Exxon Research Engineering Co | Odorless solvent manufacture |
US2859260A (en) * | 1955-05-31 | 1958-11-04 | Kellogg M W Co | Alkylation of hydrocarbons |
IL28565A (en) | 1967-08-25 | 1971-12-29 | Hydro Chem & Mineral Corp | Apparatus and process for providing direct contact between a liquid and one or more other fluids |
US3839487A (en) | 1971-07-09 | 1974-10-01 | Merichem Co | Alkylation utilizing fibers in a conduit reactor |
US3759318A (en) | 1972-03-15 | 1973-09-18 | Stratford Eng Corp | Contactor improvements |
US3999889A (en) | 1975-10-23 | 1976-12-28 | Exxon Research And Engineering Company | Mixing head |
US4650918A (en) * | 1985-11-25 | 1987-03-17 | Atlantic Richfield Company | Alkylation aide for sulfuric acid catalyzed alkylation units |
DK168520B1 (en) | 1989-12-18 | 1994-04-11 | Topsoe Haldor As | Process for liquid phase alkylation of a hydrocarbon with an olefin alkylating agent |
US5420093A (en) | 1991-10-25 | 1995-05-30 | Institut Francais Du Petrole | Catalyst based on silica and sulfuric acid and its use for the alkylation of paraffins |
EP0584006B1 (en) | 1992-08-20 | 1996-06-05 | Institut Francais Du Petrole | Process for the alkylation of paraffins |
US5750818A (en) * | 1996-06-20 | 1998-05-12 | Amoco Corporation | Alkylation process |
US5785933A (en) | 1997-01-21 | 1998-07-28 | Mobil Oil Corporation | Sulfuric acid alkylation reactor system with static mixers |
US6852902B2 (en) * | 2002-03-15 | 2005-02-08 | Catalytic Distillation Technologies | Method of removing entrained sulfuric acid from alkylate |
-
2002
- 2002-10-11 US US10/269,261 patent/US6852902B2/en not_active Expired - Fee Related
-
2003
- 2003-09-17 JP JP2004543308A patent/JP2006502282A/en active Pending
- 2003-09-17 KR KR1020057006102A patent/KR20050055755A/en not_active Application Discontinuation
- 2003-09-17 CN CNB038240750A patent/CN100488922C/en not_active Expired - Fee Related
- 2003-09-17 WO PCT/US2003/029193 patent/WO2004033697A2/en active Application Filing
- 2003-09-17 AU AU2003267259A patent/AU2003267259A1/en not_active Abandoned
- 2003-09-17 EP EP03749730A patent/EP1558549A2/en not_active Withdrawn
- 2003-09-17 CA CA002501305A patent/CA2501305A1/en not_active Abandoned
-
2004
- 2004-11-09 US US10/984,610 patent/US20050085679A1/en not_active Abandoned
- 2004-12-01 US US11/000,651 patent/US7126038B2/en not_active Expired - Fee Related
-
2005
- 2005-03-08 ZA ZA200501976A patent/ZA200501976B/en unknown
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3013093A (en) * | 1957-03-20 | 1961-12-12 | Kellogg M W Co | Alkylation process |
Also Published As
Publication number | Publication date |
---|---|
AU2003267259A8 (en) | 2004-05-04 |
WO2004033697A3 (en) | 2005-02-24 |
US20050085679A1 (en) | 2005-04-21 |
CN100488922C (en) | 2009-05-20 |
EP1558549A2 (en) | 2005-08-03 |
ZA200501976B (en) | 2006-10-25 |
US20050096493A1 (en) | 2005-05-05 |
CN1688524A (en) | 2005-10-26 |
CA2501305A1 (en) | 2004-04-22 |
JP2006502282A (en) | 2006-01-19 |
US7126038B2 (en) | 2006-10-24 |
US6852902B2 (en) | 2005-02-08 |
AU2003267259A1 (en) | 2004-05-04 |
KR20050055755A (en) | 2005-06-13 |
US20040059172A1 (en) | 2004-03-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6852902B2 (en) | Method of removing entrained sulfuric acid from alkylate | |
CA2593599C (en) | Method of removing organic sulfur compounds from alkylate | |
KR100970799B1 (en) | Paraffin alkylation | |
US8173009B2 (en) | Process for improving a hydrotreated stream | |
CN1009111B (en) | Continous process for mercaptan extraction from highly definic feed stream | |
JP2549428B2 (en) | HF alkylation and selective hydrogenation process | |
SG187607A1 (en) | Hydrodechlorination of ionic liquid-derived hydrocarbon products | |
CA2493793C (en) | Pulse flow reaction | |
EP1369465B1 (en) | Process for the alkylation of benzene | |
US4783567A (en) | HF alkylation process | |
US20210395178A1 (en) | Selective dimerization and etherification of isobutylene via catalytic distillation | |
US20120160740A1 (en) | Processes for ionic liquid catalyzed upgrading of oxygenate containing hydrocarbon feedstocks | |
RU2238928C2 (en) | Method of removing methylacetylene and propadiene from hydrocarbon streams (options) | |
US4482767A (en) | Process for production of alcohols and LPG | |
RU2220126C2 (en) | Device and method for hydrogenation | |
EP1534406B1 (en) | Contact structures | |
WO2003062178A1 (en) | Process for the utilization of refinery c4 streams | |
RU2119471C1 (en) | Method of alkylation of olefinic hydrocarbons using a catalytic mixture | |
US8502006B2 (en) | Dimerization process | |
US20060278568A1 (en) | Method of removing oxygenated sulfur compounds from hydrocarbons |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A2 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK NZ OM PH PL PT RO RU SC SD SE SG SK SL TJ TM TN TR TT TZ UA UG UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A2 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 889/DELNP/2005 Country of ref document: IN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2005/01976 Country of ref document: ZA Ref document number: 200501976 Country of ref document: ZA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2501305 Country of ref document: CA Ref document number: PA/A/2005/003627 Country of ref document: MX |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020057006102 Country of ref document: KR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2004543308 Country of ref document: JP Ref document number: 20038240750 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2003749730 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1020057006102 Country of ref document: KR |
|
WWP | Wipo information: published in national office |
Ref document number: 2003749730 Country of ref document: EP |